The published crystallographic data on cesium, rubidium, and potassium phosphates crystallizing in the NaZr 2 (PO 4 ) 3 (NZP) and langbeinite structural types are summarized and correlated. The existence of new phosphates, analogs of langbeinite mineral, is predicted. The phosphates of the suggested compositions are prepared and studied by X-ray and neutron diffraction and by IR spectroscopy. Phosphates of the formulas A 2 RM(PO 4 ) 3 , A 2 B 0.5 Zr 1.5 (PO 4 ) 3 , and ABR 2 (PO 4 ) 3 have a cubic cell, space group P2 1 3. The unit cell parameters of the phosphates in these series vary only slightly with variation of the cationic composition. Variations in the bond lengths and bond angles in the langbeinite structure depending on the cation are estimated from the results of structural studies. Cesium can be incorporated in cubic framework phosphates in an amount of up to 38 wt %. The langbeinite structure is characterized by wide possibilities of isomorphous substitutions involving large alkali and alkaline-earth metal cations arranged in the framework voids and small cations of p, d, and f elements in oxidation states 2+, 3+, and 4+, arranged in the framework positions. A specific role of lanthanides in formation of the langbeinite-type framework is noted.

The properties (behavior on heating, in aqueous solutions, and in salt melts) of orthophosphates A 2 RM(PO 4 ) 3 , A 2 B 0.5 Zr 1.5 (PO 4 ) 3 , and ABR 2 (PO 4 ) 3 [A = K, Rb, Cs; B = Mg, Sr, Ba; R = Ga, Fe, Cr, Ln (Ce3Lu)] crystallizing in the structure of langbeinite mineral (cubic system, space group P2 1 3, Z = 4) were studied and compared with those of NZP-type phosphates. The thermal transformations of the structure and the influence of temperature on the distortion of the framework-forming polyhedra were examined. The volatilization of cesium, in particular, from the solid phase in the course of its formation, was evaluated. The rates of cesium and barium leaching at 90 and 95oC were determined.